Polymeric cyclopentadiene derivatives, method for preparing and use thereof

ABSTRACT

Polymeric cyclopentadiene derivatives, method for preparing polymeric cyclopentadiene derivatives, and use of polymeric cyclopentadiene derivatives in curable binder compositions.

CROSS REFERENCE TO RELATED APPLICATION

This application is a continuation-in-part of our copending U.S. patentapplication Ser. No. 300,786 filed on Sept. 10, 1981 and entitled"Cyclopentadiene Derivatives, Method for Preparing and Use Thereof" andnow U.S. Pat. No. 4,412,088.

DESCRIPTION

1. Technical Field

The present invention is directed to new polymeric cyclopentadienederivatives which are particularly useful in binder compositions. Suchcompositions are curable at normal room temperatures. The compositionsare capable of being cured at normal room temperatures by a gaseouscuring agent or an acidic catalyst incorporated into the binder. Thecompositions of the present invention are especially useful as foundrybinders. The present invention is also directed to a method forpreparing certain polymeric derivatives of cyclopentadiene.

2. Background Art

In the foundry art, cores and molds used in making metal castings aregenerally prepared from shaped, cured mixtures of aggregate material(e.g., sand) and a binder. One of the preferred techniques of makingthese sand cores includes the basic steps of mixing the sand with aresin binder and a curing catalyst, molding the mixture to the desiredshape and allowing it to cure and solidify at room temperature withoutthe application of heat. Resins useful in this technique includefurfuryl alcohol-formaldehyde polymers, furfurylalcohol-urea-formaldehyde polymers, alkyd isocyanate resins, and sodiumsilicate binders. Such technique is commonly referred to as a "no bake"process.

Another technique employed includes the basic steps of mixing theaggregate with a resin binder, molding the mixture to the desired shape,and curing the shape by passing a gaseous catalyst through it. Thistechnique is often referred to as the "cold box" method. Binders whichare suitable for use in such processes must possess a number ofimportant characteristics. For instance, the binders must be capable ofproviding relatively high strength characteristics to the molded articleand must be capable of curing to a considerable degree at normal roomtemperatures. Also, since curing of the binders occurs while as a thinlayer of film on the aggregate and the aggregate can act as a heat sink,the curing does not necessarily proceed in the same manner as when thebinder is cured in bulk. In addition, foundry cores and molds mustretain the strength properties until the metal solidifies in the mold,but must lose such properties due to their exposure at highertemperatures so that after solidification of the metal, the cores ormolds can readily be broken down for shake-out or removal from thecasting. Accordingly, providing new binders for foundry applicationswhich contain the necessary properties is quite difficult. This problemis made more acute when the object is a relatively inexpensive binder.

It has also been discovered that fulvenes and/or fulvene prepolymerscould be employed as binders for foundry applications as described inU.S. Pat. No. 4,246,167 entitled "Foundry Binder Composition" to Grimm,et al., and assigned to Ashland Oil Inc., the assignee of the presentapplication. However, the use of such fulvenes has not been entirelysatisfactory since such are somewhat susceptible to degradation fromatmospheric oxygen and have an unpleasant odor.

In addition, applicants in copending application Ser. No. 300,786disclose certain derivatives of cyclopentadiene and/or of methylcyclopentadiene which have improved resistance to atmospheric oxygen,and reduced odor as compared to the fulvenes discussed hereinabove.

DISCLOSURE OF INVENTION

The present invention provides a process for preparing certain polymericderivatives of cyclopentadiene and/or of methyl substitutedcyclopentadiene. The present invention is also concerned with novelpolymeric derivatives of cyclopentadiene and/or of methyl substitutedcyclopentadiene which can be produced by the process of the presentinvention. The present invention is also concerned with the use ofcertain polymeric derivatives of cyclopentadiene and/or of methylsubstituted cyclopentadiene in binder compositions and especiallyfoundry binder compositions.

The polymers of the present invention have reduced odor as compared tothe fulvenes and the cyclopentadiene derivatives discussed hereinabove.Moreover, the polymers of the present invention, when used as in abinder composition for molded articles, demonstrate greater erosionresistance when compared to the use of the fulvenes and thecyclopentadiene derivatives discussed hereinabove.

The present invention is concerned with polymeric cyclopentadienederivatives having recurring units of the formula I or isomers thereofor mixtures thereof: ##STR1##

Each R₁ and R₂ individually is preferably a hydrocarbon containing 1 to10 carbon atoms, or a hydrocarbon containing one or more oxygen bridges,or a furyl group; or are interconnected and together with the carbonatom to which they are connected from a cycloaliphatic hydrocarbongroup, or one of R₁ or R₂ is hydrogen. Each R₃, R₄, R₅, R₆, and R₉individually is hydrogen or methyl or --CH₂ -- or ##STR2## provided thatat least two (2) of R₃, R₄, R₅, R₆, and R₉ are hydrogen. It is furtherprovided that at least two of said R₃, R₅, R₆, and R₄ or R₉ are --CH₂--. When R₄ is --CH₂ --, then R₉ is other than --CH₂ -- and vice versa.Each R₇ and R₈ individually is a hydrocarbon group containing 1-10carbon atoms or a hydrocarbon group containing one or more oxygenbridges in the chain and containing up to 10 carbon atoms, or areinterconnected and together with the carbon atom to which they areconnected, form a cycloaliphatic hydrocarbon group, or furyl, or one ofR₇ or R₈ is hydrogen. In addition, n is an integer of at least 2.

The present invention is also concerned with a curable composition whichincludes at least one polymeric cyclopentadiene derivative of the typediscussed hereinabove, and an acidic catalyst. The acidic catalyst has apKa of about 4 or less. The acidic catalyst is incorporated into thecomposition prior to molding or is provided by passing a gas through themolded composition.

The present invention is also concerned with molding compositions whichinclude a major amount of aggregate and an effective bonding amount upto about 40% by weight of the aggregate of the above-defined curablecomposition.

The present invention is also directed to a process for the fabricationof molded articles which includes the following steps:

(a) mixing aggregate with a bonding amount up to about 40% by weightbased upon the weight of the aggregate of a binder composition of thetype described hereinabove which contains the acidic catalyst;

(b) introducing the composition obtained from step (a) into a pattern;

(c) hardening the composition in the pattern to become self-supporting;and

(d) thereafter removing the shaped article of step (c) from the patternand allowing it to further cure, thereby obtaining a hardened, solid,cured, molded article.

The present invention is also concerned with a process for thefabrication of molded articles which comprises:

(a) mixing the aggregate with a bonding amount up to about 40% by weightbased upon the weight of the aggregate of a polymeric cyclopentadienederivative of the type discussed hereinabove;

(b) introducing the composition obtained from step (a) into a pattern;

(c) hardening the composition in the pattern to become self-supportingby passing an acidic gas through the composition; and

(d) thereafter removing the shaped article of step (c) from the patternand allowing it to further cure, thereby obtaining a hardened, solid,cured, molded article.

The present invention is also concerned with a process for casting ametal which includes fabricating a shape as described hereinabove,pouring metal while in the liquid state into or around the shape,allowing the metal to cool and solidify, and then separating the moldedmetal article.

The present invention is also concerned with a process for preparingpolymeric cyclopentadiene derivative which comprises reactingcyclopentadiene derivative having the formula: ##STR3## isomers, ormixtures thereof; wherein each R₁ and R₂ individually is a hydrocarboncontaining 1 to 10 carbon atoms or a hydrocarbon containing one or moreoxygen bridges in the chain and contains up to 10 carbon atoms; or areinterconnected and together with the carbon atom to which they areconnected, form a cycloaliphatic hydrocarbon group or one or R₁ or R₂ ishydrogen; each R₃, R₄, R₅, R₆, and R₉ individually is hydrogen, methyl,or ##STR4## or R₄ or R₉ or R₅ is ##STR5## wherein each R₇ and R₈individually is a hydrocarbon containing 1 to 10 carbon atoms or ahydrocarbon containing one or more oxygen bridges in the chain andcontaining up to 10 carbon atoms; or are interconnected and togetherwith the carbon atom to which they are connected form a cycloaliphatichydrocarbon group or furyl or one of R₇ or R₈ is hydrogen, and providedthat at least four of R₃, R₄, R₅, R₆, and R₉ are hydrogen; withformaldehyde in the presence of a basic catalyst to provide a polymericcyclopentadiene derivative.

Moreover, the present invention is directed to polymeric cyclopentadienederivatives obtained by the process described hereinabove.

BEST AND VARIOUS MODES FOR CARRYING OUT THE INVENTION

The polymeric cyclopentadiene derivatives of the present invention arerepresented by the recurring formula I below or isomers or mixturesthereof: ##STR6##

Each R₁ and R₂ individually is a hydrocarbon group containing 1 to 10carbon atoms such as an alkyl, aryl, alkaryl, or aralkyl group; or afuryl group; or are interconnected and together with the carbon atom towhich they are connected, form a cycloaliphatic hydrocarbon group or ahydrocarbon group containing one or more oxygen bridges in the chaincontaining up to 10 carbon atoms; or one of R₁ or R₂ is hydrogen.

The hydrocarbon groups can be free from non-benzenoid unsaturation orcan include ethylenic unsaturation. Examples of some hydrocarbon groupsinclude alkyl groups, such as methyl, ethyl, propyl, amyl and butyl;aryl groups, such as phenyl and naphthyl; alkaryl groups, such asbenzyl; aralkyl groups; and ethylenically unsaturated groups, such asvinyl. Examples of some cyclic groups include cycloaliphatic groups,such as cyclopentyl, cyclohexyl, and cycloheptyl.

Preferably at least one of R₁ and R₂ is methyl and the other is an alkylof 2 to 5 carbon atoms.

Each R₃, R₄, R₅, R₆, and R₉ individually is hydrogen or methyl or##STR7## or R₄ or R₅ or R₉ is: ##STR8##

At least two of R₃, R₄, R₅, R₆, and R₉ are hydrogen. At least two ofsaid R₃, R₅, R₆, and R₄ or R₉ are --CH₂ --. Each R₇ and R₈ individuallyis a hydrocarbon group containing 1 to 10 carbon atoms, or a hydrocarbongroup containing one or more oxygen bridges in the chain containing upto 10 carbon atoms, or are interconnected and together with the carbonatom to which they are connected form a cycloaliphatic hydrocarbongroup, or furyl, or one of R₇ or R₈ is hydrogen. Preferably, at leastone of R₇ and R₈ differs from R₁ and R₂. The preferred R₇ and R₈ groupsare alkyl, more preferably at least one R₇ and R₈ is methyl. When a##STR9## group is present, such is preferably at the R₄ or R₅ or R₉position.

In addition, if excess aldehyde or ketone is employed in the preparationof the monomeric cyclopentadiene derivatives, such could containcompounds wherein R₄ or R₉ or R₅ can have the structure: ##STR10##

In such a case, R₃ and R₆ will be as previously described.

An example of an isomer of formula I above can be represented by thestructure: ##STR11##

Examples of some cyclopentadiene derivatives from which the polymericcyclopentadiene derivatives of the present invention can be obtainedinclude fulvenes such as methylisobutylfulvene (R₁ is methyl; R₂ isisobutyl; R₃, R₄, R₅, and R₆ are H); cyclohexylfulvene (R₁ and R₂ areinterconnected and form a cyclohexyl ring with the common carbon atom towhich they are connected; R₃, R₄, R₅, and R₆ are H); methylethylfulvene(R₁ is methyl; R₂ is ethyl; R₃, R₄, R₅, and R₆ are H); diphenylfulvene(R₁ and R₂ are phenyl; R₃, R₄, R₅, and R₆ are H); furylfulvene (R₁ isfuryl; R₂ is H; and R₃, R₄, R₅, and R₆ are H); diisobutylfulvene (R₁ andR₂ are isobutyl; R₃, R₄, R₅, and R₆ are H); isophorone fulvene (R₁ andR.sub. 2 are interconnected and form an isophorone ring with the commoncarbon atom to which they are connected; R₃, R₄, R₅, and R₆ are H).

Fulvenes have been known for many years as well as their method ofpreparation. Also, it has been known that fulvenes polymerize in thepresence of acids.

Suggestions of methods for preparing fulvenes can be found in U.S. Pat.Nos. 2,589,969; 3,051,765; and 3,192,275. In addition, fulvenes can bepurified by distillation according to a method by Kice, J.A.C.S. 80,3792 (1958), and the method of McCaine, J. Chem. Society 23, 632 (1958).

The polymeric cyclopentadiene derivatives of the present invention canbe prepared by reacting a fulvene of the formula: ##STR12## wherein eachR'₇ and R'₈ is the same as R₇ and R₈ respectively as definedhereinabove. Each R'₃, R'₄, R'₅, and R'₆ individually is hydrogen ormethyl provided that a maximum of only one such R'₃, R'₄, R'₅, and R'₆is methyl, and, in addition, if excess aldehyde or ketone is employed inthe preparation of the fulvene, R'₄ or R'₅ can have the structure:##STR13##

In such a case, R₃ and R₆ will be as previously discussed.

The fulvene can be prepared by reacting cyclopentadiene and/ormethylcyclopentadiene with a carbonyl compound from the group ofaldehyde or ketone in the presence of a basic catalyst. The preferredcarbonyl compounds have 1 to 8 carbon atoms and more preferably, areketones having a hydrogen on the alpha carbon atom, and most preferably,are ketones with at least one methyl group. The reaction is generallycarried out at temperatures of about 40°-90° C. and preferably, at about50°-80° C. Examples of some basic catalysts include: strong bases (e.g.KOH), an amine, and basic ion exchange resins. Suggestions of methodsfor preparing fulvenes can be found in U.S. Pat. Nos. 2,589,969;3,051,765; and 3,192,276. Suggestions of preparing fulvene polymers canbe found in U.S. Pat. Nos. 2,512,698; 2,587,791; 2,898,325; and3,390,156. The amount of catalyst employed is usually about 20 to about50 mole percent based on the moles of cyclopentadiene ormethylcyclopentadiene used.

About stoichiometric amounts (e.g.-a maximum of about a 10% excess ofeither reactant) is usually employed. The reaction is preferably carriedout in an alcoholic solution. The reaction usually takes about 0.5 toabout 3 hours. The amount of diluent (e.g. alcohols such as methanol,ethanol, isopropanol, n-propanol, butanols, and amyl alcohol) is usuallyabout 50 to about 150 ml per mole of cyclopentadiene ormethylcyclopentadiene. The preferred alcohols employed have three ormore carbon atoms. Most preferably a mixture of methanol with suchhigher alcohols having three or more carbon atoms is employed.

Polymeric derivatives within the scope of the present invention can beprepared by either of the following two procedures:

1. The reaction product from the above discussed type of reaction(i.e.-the fulvene) is reacted with formaldehyde as will be discussedherein below to provide the polymers of the present invention.

2. The reaction product from the above discussed type of reaction(i.e.-the fulvene) is reacted with a carbonyl compound in general(e.g.-acetone,methylethylketone and methylisobutyl ketone) to provide adisubstituted cyclopentadiene of the type disclosed in application300,786, disclosure of which is incorporated herein by reference. Thisreaction is also carried out in the presence of a basic catalyst of thetype and amounts discussed hereinabove employed to prepare the fulvenes.

The preferred carbonyl compounds contain 1-8 carbon atoms and preferablyare ketones containing at least one methyl group. The most preferredketone is acetone.

This reaction is generally carried out at temperatures of about 40°-90°C. and preferably at about 60°-80° C. About stoichiometric amounts(e.g.-about a maximum of a 10% excess of either reactant) are usuallyemployed. However, when acetone is used as the only carbonyl compound inboth stages of the process, at least about 2 times the stoichiometricamount (i.e. 4 moles per mole of cyclopentadiene ormethylcyclopentadiene) of acetone is preferably employed. And morepreferred at least about 3 times, and most preferred about 3 to about 5times the stoichiometric amount is employed. This reaction is preferablycarried out in an alcoholic solution. The reaction usually takes about 5to about 24 hours. The amounts of catalyst and diluent are usuallywithin the same range as those amounts employed in preparing thefulvene.

By following the above process, a mixture containing about 30-60% ofdisubstituted cyclopentadiene derivatives of the type disclosed in saidapplication, 300,786, can be obtained.

The reaction products containing the disubstituted cyclopentadienederivatives is reacted with formaldehyde as will be discussed hereinbelow to provide the polymers of the present invention.

Mixtures of any of the above fulvenes and/or disubstitutedcyclopentadiene derivatives can be employed, if desired.

The fulvene and/or disubstituted cyclopentadiene derivative is thenreacted with formaldehyde to provide the polymeric derivatives of thepresent invention. Generally about 0.1 to about 1 moles of formaldehydeand preferably about 0.25 to about 0.75 moles of formaldehyde areemployed for each mole of cyclopentadiene type reactant.

The formaldehyde employed is preferably in the form of a methanolsolution. However, other forms capable of supplying formaldehyde to thereaction mass such as paraformaldehyde and trioxane can be employed.

Paraformaldehyde is a substantially water-free source of formaldehydeand is a mixture of polyoxymethylene glycol which usually contains fromabout 90 to about 99% by weight of formaldehyde with the balanceconsisting principally of free and combined water. It is recognized, ofcourse, that paraformaldehyde can include mixtures of polyoxymethyleneglycols containing down to about 80% formaldehyde with the balanceconsisting principally of free and combined water, as long as themixture is still a solid material. Usually, commercial grades ofparaformaldehyde contain from about 91 to about 98% formaldehyde. Thechemical composition of paraformaldehyde can be expressed by thefollowing formula:

    HO(CH.sub.2 O).sub.n H

wherein n is equal to 8 to 100. Normally, the majority of thepolyoxymethylene glycols in paraformaldehyde contain over about 12formaldehyde units per molecule. Paraformaldehyde has a melting point offrom about 120° to about 170° C.

This reaction is also carried out in the presence of a basic catalyst ofthe type and amounts discussed hereinabove employed to prepare thefulvenes.

This reaction is generally carried out at temperatures of about 60°-90°C. and preferably at about 60°-80° C. This reaction is preferablycarried out in an alcoholic solution. The reaction usually takes about 5to about 24 hours. The amounts of catalyst and diluent are usuallywithin the same range as those amounts employed in preparing thefulvene.

By following the above procedures, the polymeric derivatives of thepresent invention are obtained. The polymeric derivatives preferablyhave molecular weights of about 350 to about 1525, and preferably n informula I is an integer of about 2 to about 9.

Furthermore, the polymers can be reacted with ketones and preferablyacetone in the presence of a basic catalyst under the same conditions asdescribed hereinabove for the reaction of the fulvenes with the carbonylcompound to provide the disubstituted cyclopentadiene derivatives.

The polymers preferably are fluid enough so that when applied either perse or in admixture with the diluents will flow to coat the aggregateused.

The polymeric cyclopentadiene derivatives of the present invention areespecially useful in binder compositions and particularly foundry bindercomposition. Mixtures of the polymeric cyclopentadiene derivatives canbe used.

In addition, the binder composition of the present invention contains anacidic catalyst. The acidic catalysts employed have a pKa value of about4 or less and include organic acids such as formic acid, oxalic acid,and the organic substituted sulfonic acids such as benzenesulfonic acidand toluenesulfonic acid, and preferably Lewis acids such as BF₃. Theacidic catalyst can be provided in the foundry mix before molding(e.g.--"no bake" process), and/or by passing a gas through the moldedcomposition such as an acid per se or a gas such as SO₂ which inconjunction with a component of the molded composition (e.g. a peroxide)forms an acid in situ.

The acidic catalyst when already in the mix prior to molding isgenerally present in amounts up to a maximum of about 5% by weight basedupon the amount of binder employed. The minimum amount of acidiccatalyst is usually about 0.8 percent based upon the amount of binderemployed. When employing a "cold box" process usually up to about 5seconds of gassing time is sufficient.

The polymeric cyclopentadiene derivatives can be employed in combinationwith fulvenes of the type discussed hereinabove, and/or withdisubstituted cyclopentadiene derivatives and/or prepolymers thereof asdiscussed in U.S. Pat. Ser. No. 300,786, and/or with furfuryl alcoholand/or furan prepolymer foundry binder systems, and/or epoxy polymersand/or phenolic materials such as phenol, substituted phenols orphenolformaldehyde condensates.

The furan propolymers include reaction products of furfuryl alcohol andof aldehydes such as formaldehyde. In addition, the aldehyde-furfurylalcohol reaction product can be modified with varying amounts ofreactants such as urea. The mole ratios of formaldehyde to furfurylalcohol which can be employed can vary widely. For instance, the furanpolymer can be prepared from about 0.4 to about 4 moles of furfurylalcohol per mole of formaldehyde, and preferably from about 0.5 to about2 moles of furfuryl alcohol per mole of formaldehyde.

The furan polymer which can be employed in the present invention can beany of the various furan polymers which are known to be suitable formolding and especially foundry purposes. Examples of such furan polymersinclude those obtained from about 1 mole of urea, about 0.2 to 2 molesof furfuryl alcohol and about 1 to 3 moles of formaldehyde such asdescribed in U.S. Pat. Nos. 3,222,315 and 3,247,556. Other suitablefuran polymers are disclosed in U.S. Pat. No. 3,346,534. The furanpolymers are usually prepared by polymerization in the presence of anacid catalyst. Usually when a furan polymer is employed, it is addedtogether with furfuryl alcohol.

Examples of suitable epoxy polymers include epoxidized novolak polymers,glycidyl ethers of a polynuclear dihydric phenol, and reaction productsthereof with polymers terminated with reactive groups. Preferably theepoxies employed are liquid. The preferred types of epoxy polymers arethe polyepoxides of epichlorohydrin and bisphenol-A, i.e.,2,2-bis(p-hydroxyphenyl) propane. Other suitable epoxies as statedhereinabove include those obtained by reacting a polynuclear dihydricphenol with haloepoxy alkane in general.

Suitable polynuclear dihydric phenols can have the formula: ##STR14##wherein Ar is an aromatic divalent hydrocarbon such as naphthalene and,preferably, phenylene, A and A₁ which can be the same or different arealkyl radicals, preferably having from 1 to 4 carbon atoms, halogenatoms, e.g., fluorine, chlorine, bromine and iodine, or alkoxy radicals,preferably having from 1 to 4 carbon atoms, x and y are integers havinga value 0 to a maximum value corresponding to the number of hydrogenatoms on the aromatic radical (Ar) which can be replaced by substituentsand R' is a bond between adjacent carbon atoms as in dihydroxydiphenylor is a divalent radical including, for example: ##STR15## --O--, --S--,--SO₂ -- and --S--S-- and divalent hydrocarbon radicals, such asalkylene, alkylidene, cycloalipahtic, e.g., cycloalkylene, halogenated,alkoxy or aryloxy substituted alkylene, alkylidene and cycloalophaticradicals as well as aromatic radicals including halogenated, alkyl,alkoxy or aryloxy substituted aromatic radicals and a ring fused to anAr group; or R' can be polyalkoxy, or polysiloxy, or two or morealkylidene radicals separated by an aromatic ring, a tertiary aminogroup, an ether linkage, a carbonyl group or a sulfur containing groupsuch as sulfoxide, and the like.

Examples of specific dihydric polynuclear phenols include among others,the bis-(hydroxyphenyl) alkanes such as 2,2-bis-(4-hydroxyphenyl)propane, bis-(2-hydroxyphenyl) methane, bis-(4-hydroxyphenyl) methane,bis-(4-hydroxy-2,6-dimethyl-3-methoxyphenyl) methane,1,1-bis-(4-hydroxyphenyl) ethane, 1,2-bis-(4-hydroxyphenyl) ethane,1,1-bis(4-hydroxy-2-chlorophenyl) ethane,1,1-bis-(3-methyl-4-hydroxyphenyl) propane,2,2-bis-(3-phenyl-4-hydroxyphenyl) propane,2,2-bis(2-isopropyl-5-hydroxyphenyl) propane, 2,2-bis(4-hydroxynaphthyl)pentane, bis-(4-hydroxyphenyl) phenylmethane, bis-(4-hydroxyphenyl)cyclohexylmethane, 1,2-bis-(4-hydroxyphenyl)-1-phenyl propane;di(hydroxyphenyl) sulfones such as bis(4-hydroxyphenyl) sulfone, 2,4'dihydroxydiphenyl sulfone, 5'-chloro-2,4'-dihydroxydiphenyl sulfone, and5'-chloro-2,2'-dihydroxydiphenyl sulfone, and5'-chloro-4,4'-dihydroxydiphenyl sulfone; di(hydroxyphenyl) ethers suchas bis-(4-dihydroxy-phenyl) ether, the 4,3'-, 4,2'-, 2,2'-, 3,3'-,2,3'-, dihydroxydiphenyl ethers, 4,4'-dihydroxy-3,6-dimethyldiphenylether, bis-(4-hydroxy-3-isobutylphenyl) ether,bis-(4-hydroxy-3-isopropylphenyl) ether, bis-(4-hydroxy-3-chlorophenyl)ether, bis-(4-hydroxy-3-fluorophenyl) ether,bis-(4-hydroxy-3-bromophenyl) ether, bis-(4-hydroxynapthyl) ether,bis-(4-hydroxy-3-chloronaphthyl) ether, bis-(2-hydroxydiphenyl) ether,4,4'-dihydroxy-2,6-dimethoxy-diphenyl ether, and 4,4'-dihydroxy-2,5-diethoxydiphenyl ether.

The preferred dihydric polynuclear phenols are represented by theformula: ##STR16## wherein A and A₁ are as previously defined, x and yhave values from 0 to 4 inclusive and R₁ is a divalent saturatedaliphatic hydrocarbon radical, particularly alkylene and alkylideneradicals having from 1 to 3 carbon atoms and cycloalkylene radicalshaving up to and including 10 carbon atoms. The most preferred dihydricphenol is bisphenol-A, i.e., 2,2-bis(p-hydroxyphenyl) propane.

The halo-epoxy alkane can be represented by the formula: ##STR17##wherein X is a halogen atom (e.g., chlorine and bromine), each R₂individually is hydrogen or alkyl group of up to 7 carbon atoms; whereinthe number of carbon atoms in any epoxy alkyl group generally totals nomore than 10 carbon atoms.

While glycidyl ethers, such as derived from epichlorohydrin, areparticularly preferred, the epoxy polymers containing epoxy-alkoxygroups of a greater number of carbon atoms are also suitable. These areprepared by substituting for epichlorohydrin such representativecorresponding chlorides or bromides of monohydroxy epoxyalkanes as1-chloro-2,3-epoxybutane, 2-chloro-3,4-epoxybutane,1-chloro-2-methyl-2,3-epoxypropane, 1-bromo-2,3-epoxypentane,2-chloromethyl-1,2-epoxybutane, 1-bromo-4-ethyl-2,3-epoxypentane,4-chloro-2-methyl-2,3-epoxypentane, 1-chloro-2,3-epoxyoctane,1-chloro-2-methyl-2,3-epoxyoctane, or 1-chloro-2,3-epoxydecane.

The epoxidized novolaks can be represented by the formula: ##STR18##wherein n is at least about 0.2; E is hydrogen or an epoxyalkyl group,at least two E groups per polymer molecule being an epoxyalkyl group andwherein the epoxyalkyl group is represented by the formula: ##STR19##

R₃ is hydrogen or alkyl or alkylene or aryl or aralkyl or alkaryl orcycloalkyl or furyl group; each R₂ individually is hydrogen or alkylgroup of up to 7 carbon atoms; wherein the number of carbon atoms in anyepoxyalkyl group totals no more than 10 carbon atoms; each X and Y isindividually hydrogen or chlorine or alkyl or hydroxyl; each R₄individually is hydrogen or chlorine or a hydrocarbon group. Preferably,substantially all of the E groups are epoxyalkyl groups. Generally R₃,X, Y, and R₄ when hydrocarbons, contain no more than about 12 carbonatoms.

The epoxy novolaks can be prepared by known methods by the reaction of athermoplastic phenolic-aldehyde polymer of a phenol having the formula:##STR20## wherein X, Y, and R₄ have the meaning as defined above with ahalo-epoxy alkane of the formula: ##STR21## wherein X is a halogen atom(e.g., chlorine, bromine, and the like) and R₂ have the same meanings asdefined hereinabove.

Hydrocarbon-substituted phenols having two available positions ortho orpara to a phenolic hydroxy group for aldehyde condensation to providepolymers suitable for the preparation of epoxy novolaks include o- andp-cresols, o- and p-ethyl phenols, o- and p-isopropyl phenols, o- andp-sec-butyl phenols, o- and p-amyl phenols, o- and p-octyl phenols, o-and p-nonyl phenols, 2,5-xylenol, 3,4-xylenol, 2,5-diethyl phenol,3,4-diethyl phenol, 2,5-diisopropyl phenol, 4-methyl resorcinol, 4-ethylresorcinol, 4-isopropyl resorcinol, 4-tert-butyl resorcinol, o- andp-benzyl phenols, o- and p-phenethyl phenols, o- and p-phenyl phenols,o- and p-tolyl resorcinol, and 4-cyclohexyl resorcinol.

Various chloro-substituted phenols which can also be used in thepreparation of phenol-aldehyde resins suitable for the preparation ofthe epoxy novolaks include o- and p-chloro-phenols, 2,5-dichloro phenol,2,3-dichloro phenol, 3,4-dichloro phenol, 2-chloro-3-methyl phenol,2-chloro-5-methyl-phenol, 3-chloro-2-methyl phenol, 5-chloro-2-methylphenol, 3-chloro-4-ethyl phenol, 4-chloro-3-methyl phenol,4-chloro-3-ethyl phenol, 4-chloro-3-isopropyl phenol, 3-chloro-4-phenylphenol, 3-chloro-4-chlorophenyl phenols, 3,5-dichloro-4-methyl phenol,3,5-dichloro-2-methyl phenol, 2,3-dichloro-5-methyl phenol,2,5-dichloro-3-methyl phenol, 3-chloro-4,5-dimethyl phenol,4-chloro-3,5-dimethyl phenol, 2-chloro-3,5-dimethyl phenol,5-chloro-2,3-dimethyl phenol, 5-chloro-3,4-dimethyl phenol,2,3,5-trichloro phenol, 3,4,5-trichloro phenol, 4-chloro resorcinol,4,5-dichloro resorcinol, 4-chloro-5-methyl resorcinol, and5-chloro-4-methyl resorcinol.

Typical phenols which have more than two positions ortho or para to aphenolic hydroxy group available for aldehyde condensation and which, bycontrolled aldehyde condensation, can also be used are: phenol,m-cresol, 3,5-xylenol, m-ethyl and m-isopropyl phenols, m,m'-diethyl andm,m'-diisopropyl phenols, m-butylphenols, m-amyl phenols, m-octylphenols, m-nonyl phenols, resorcinol, 5-methyl-resorcinol, and 5-ethylresorcinol.

As condensing agents any aldehyde may be used which will condense withthe particular phenol being used, including formaldehyde, acetaldehyde,propionaldehyde, butyraldehyde, heptaldehyde, benzaldehyde, andalkyl-substituted benzaldehydes, such as toluic aldehyde; napthaldehyde,furfuraldehyde, glyoxal, acrolein, or compounds capable of engenderingaldehydes such as para-formaldehyde and hexamethylene tetramine. Thealdehydes can also be used in the form of a solution, such as thecommercially available formalin.

While glycidyl ethers, such as derived from epichlorohydrin, arepreferred, the epoxy novolak polymers can contain epoxy-alkoxy groups ofa greater number of carbon atoms. These are prepared by substituting forepichlorohydrin such representative corresponding chlorides or bromidesof monohydroxy epoxyalkanes as 1-chloro-2, 3-epoxybutane, 2-chloro-3,4-epoxybutane, 1-chloro-2-methyl-2, 3-epoxypropane, 1-bromo-2,3-epoxypentane, 2-chloromethyl-1, 2-epoxybutane, 1-bromo-4-ethyl-2,3-epoxypentane, 4-chloro-2-methyl-2, 3-epoxypentane, 1-chloro-2,3-epoxyoctane, 1-chloro-2-methyl-2, 3-epoxyoctane, or 1-chloro-2,3-epoxydecane.

Preferred epoxidized novolaks are represented by the formula: ##STR22##wherein n is at least about 0.2. The epoxidized novolak preferably isliquid and preferably n is less than about 1.5.

Examples of reaction products of glycidyl ethers with polymersterminated with reactive groups include reaction products of glycidylether of bisphenol-A and epichlorohydrin with telechelic prepolymers(i.e., prepolymers having the reactive groups capable of producingstrong elastomeric structures). The prepolymers are usually liquids.Examples of some polymer chains include polysulfide, polyisobutylene;polybutadiene, butadiene-acrylonitrile copolymer, polyamide, polyetherand polyester. The reactive terminal groups include thiol, carboxyl,hydroxyl, amine, and isocyanate. A preferred telechelic prepolymer iscarboxyl terminated butadiene-acrylonitrile prepolymer. Also, suitableepoxy polymers include epoxidized unsaturated oils such as epoxidizedlinseed and soybean oil. Such preferably have an oxirane content ofabout 7 to about 8% by weight.

When the polymeric cyclopentadiene derivatives are employed in admixturewith other materials of the type discussed above as auxiliary binders,such as furfuryl alcohol and/or disubstituted cyclopentadienederivatives, and/or fulvenes, and/or furan polymers and/or phenolicsand/or epoxy polymers, such polymeric cyclopentadiene derivatives aregenerally employed in amounts of about 90 to about 50% by weight basedupon the total amount of polymeric cyclopentadiene derivative and othermaterials defined above.

In addition, the compositions can contain a dialkyl ester of theformula:

    R.sub.1 OOC(CH.sub.2).sub.n COOR.sub.2

wherein each R₁ and R₂ individually is an alkyl of 1 to 20 carbon atomsand n is a whole number integer of 0 to 4. The ester may be blended withthe binder and/or sand and/or in conjunction with the acidic catalyst.Suitable esters include dimethyl oxalate, diethyl oxalate, dimethylsuccinate, methyl-ethyl succinate, methyl-n-propyl succinate, methylisopropyl succinate, methyl-n-butyl succinate, diethyl succinate,ethyl-n-propyl succinate, diisopropyl succinate, dibutyl succinate,dimethyl glutarate, methylethyl glutarate, methyl-n-butyl glutarate,methyl-isobutyl glutarate, diethyl glutarate, ethyl-n-propyl glutarate,diisopropyl glutarate, dibutyl glutarate, dimethyl adipate, methylethyladipate, methyl-n-propyl adipate, methylisopropyl adipate, diethyladipate, dipropyl adipate, dibutyl adipate, dioctyl succinate, dioctyladipate, octyl-nonyl glutarate, diheptyl glutarate, didecyl adipate,dicapryl adipate, dicapryl succinate, dicapryl glutarate, dilauryladipate, dilauryl succinate, dilauryl glutarate and malonic acid esters.

Preferred esters for use are the oxalates; dimethyl glutarate such asavailable from DuPont under the trade designation DBE-5; dimethyladipate available from DuPont under the trade designation DBE-6; andmixtures of such esters such as are available from DuPont under thetrade designation DBE. Other diluents can be employed if desired andinclude such groups of compounds as ketones such as acetone, methylethylketone and diisoamylketone; ketoacid esters such as ethyl acetoacetateand methyl acetoacetate; and other esters such as the cellosolve esters.

The diluent may generally be employed in an amount of from about 0.5 to30% and preferably 1.0 to 10% by weight of the binder.

When preparing an ordinary sand-type foundry shape, the aggregateemployed has a particle size large enough to permit sufficient porosityin the foundry shape to permit escape of volatiles from the shape duringthe casting operation. The term "ordinary sand-type foundry shapes" asused herein refers to foundry shapes which have sufficient porosity topermit escape of volatiles from it during the casting operation.Generally, at least about 80%, and preferably about 90%, by weight ofaggregate employed for foundry shapes has an average particle size nosmaller than about 150 mesh (Tyler screen mesh). The aggregate forfoundry shapes preferably has an average particle size between about 50and about 150 mesh (Tyler screen mesh). The preferred aggregate employedfor ordinary foundry shapes is silica sand wherein at least about 70weight percent, and preferably at least about 85 weight percent of thesand is silica. Other suitable aggregate materials include zircon,olivine, aluminosilicate sand, chromite sand and the like.

When preparing a shape for precision casting, the predominant portion,and generally at least about 80% of the aggregate, has an averageparticle size no larger than about 150 mesh (Tyler screen mesh).Preferably at least about 90% by weight of the aggregate for precisioncasting applications has a particle size no larger than 150 mesh andpreferably between 325 mesh and 200 mesh. The preferred aggregatesemployed for precision casting applications are fused quartz, zirconsands, magnesium silicate sands such as olivine, and aluminosilicatesands.

Shapes for precision casting differ from ordinary sand-type foundryshapes in that the aggregate in shapes for precision casting can be moredensely packed than the aggregate in shapes for ordinary sand-typefoundry shapes. Therefore, shapes for precision casting must be heatedbefore being utilized to drive off volatizable material present in themolding composition. If the volatiles are not removed from a precisioncasting shape before use, vapor created during casting will diffuse intothe molten melt, since the shape has a relatively low porosity. Thevapor diffusion would decrease the smoothness of the surface of theprecision cast article.

When preparing a refractory, such as a ceramic, the predominant portionand at least about 80% by weight of the aggregate employed has anaverage particle size under 200 mesh and preferably no larger than 325mesh. Preferably at least about 90% by weight of the aggregate for arefractory has an average particle size under 200 mesh, and preferablyno larger than 325 mesh. The aggregate employed in the preparation ofrefractories must be capable of withstanding the curing temperatures,such as above about 1500° F. which are needed to cause sintering forutilization.

Examples of some suitable aggregate employed for preparing refractoriesinclude the ceramics, such as refractory oxides, carbides, nitrides, andsilicides, such as aluminum oxide, lead oxide, chromic oxide, zirconiumoxide, silica, silicon carbide, titanium nitride, boron nitride,molybdenum disilicide, and carbonaceous material, such as graphite.Mixtures of the aggregates can also be used, when desired, includingmixtures of metals and the ceramics.

Examples of some abrasive grains for preparing abrasive articles includealuminum oxide, silicon carbide, boron carbide, corundum, garnet, emeryand mixtures thereof. The grit size is of the usual grades as graded bythe United States Bureau of Standards. These abrasive materials andtheir uses for particular jobs are understood by persons skilled in theart and are not altered in the abrasive articles contemplated by thepresent invention. In addition, inorganic filler can be employed alongwith the abrasive grit in preparing abrasive articles. It is preferredthat at least about 85% of the inorganic fillers has an average particlesize no greater than 200 mesh. It is most preferred that at least about95% of the inorganic filler has an average particle size no greater than200 mesh. Some inorganic fillers include cryolite, fluorospar, silicaand the like. When an organic filler is employed along with the abrasivegrit, it is generally present in amounts from about 1 to about 30% byweight based upon the combined weight of the abrasive grit and inorganicfiller.

In molding compositions, the aggregate constitutes the major constituentand the binder constitutes a relatively minor amount. In ordinary sandtype foundry applications, the amount of binder is generally no greaterthan about 10% by weight and frequently within the range of about 0.5 toabout 7% by weight based upon the weight of the aggregate. Most often,the binder content ranges from about 0.6 to about 5% by weight basedupon the weight of the aggregate in ordinary sand type foundry shapes.

In molds and cores for precision casting application the amount ofbinder is generally no greater than about 40% by weight and frequentlywithin the range of about 5 to about 20% by weight based upon the weightof the aggregate.

In refractories, the amount of binder is generally no greater than about40% by weight and frequently within the range of about 5% to about 20%by weight based upon the weight of the aggregate.

In abrasive articles, the amount of binder is generally no greater thanabout 25% by weight and frequently within the range of about 5% to about15% by weight based upon the weight of the abrasive material or grit.

A valuable additive to the binder compositions of the present inventionin certain types of sand is a silane having the general formula:##STR23## wherein R' is a hydrocarbon radical and preferably an alkylradical of 1 to 6 carbon atoms and R is a hydrocarbon group such as avinyl group or an alkyl radical; an alkoxy-substituted alkyl radical; oran alkyl-aminesubstituted alkyl radical in which the alkyl groups havefrom 1 to 6 carbon atoms. The aforesaid silane when employed inconcentrations of about 0.05 to 2% based on the binder component of thecomposition improves the humidity resistance of the system.

Examples of some commercially available silanes are Dow Corning Z6040;Union Carbide A187 (gamma glycidoxy propyltrimethoxy silane); UnionCarbide A1100 (gamma amino-propyltriethoxy silane); Union Carbide A1120[N-beta (amino-ethyl)-gamma aminopropyltrimethoxy silane];vinyltriethoxysilane; and Union Carbide A186(beta-3,4-epoxy-cyclohexyl)-ethyltrimethoxysilane.

When the compositions of the present invention are used to prepareordinary sand-type foundry shapes, the following steps are employed:

1. Forming a foundry mix containing an aggregate (e.g., sand) and thebonding agent;

2. Introducing the foundry mix into a mold or pattern to thereby formthe desired shape.

3. Allowing the shape to obtain a minimum strength in the mold; and

4. Thereafter removing the shape from the mold or pattern allowing it tofurther cure thereby obtaining a hard solid cured foundry shape.

The foundry mix can optionally contain other ingredients such as ironoxide, ground flax fibers, wood cereals, pitch, refractory flours, andthe like.

The systems of the present invention can be used for the casting of therelatively high melting point ferrous-type metals such as iron and steelwhich are poured at about 2500° F., as well as for the casting of therelatively low melting point nonferrous type metals such as aluminum,copper, and copper alloys including brass.

In order to further understand the present invention, the followingnon-limiting examples concerned with foundry are provided. All parts areby weight unless the contrary is stated. The foundry samples are curedby the so-called "no-bake" process.

Examples 1 to 8 represent preparations of polymeric cyclopentadienederivatives of the present invention:

EXAMPLE 1

Into a 3-neck flask equipped with a stirrer, condenser, thermometer andN₂ -inlet are added about 112 grams of KOH dissolved in about 250 ml ofisopropanol and 150 ml of methanol. At room temperature, about 347 grams(about 5.25 moles) of freshly distilled cyclopentadiene, which is keptat the temperature of dry ice/acetone, are added and the mixture isallowed to warm up to about 20° C. Next, 570 grams (about 5 moles) ofmethylamyl-ketone are added at a rate of about 35 ml/minute. Thereaction is exothermic and the temperature increases to about 70° C.After the addition is completed, the temperature is held at about 70° C.for about 75 minutes. Then about 1.25 moles of formaldehyde at a 55%solution in a mixture of 92% methanol and 8% water are added over aperiod of about 10 minutes. The temperature increases to about 78° C.and reflux can be observed. When all of the formaldehyde is added, thetemperature is held at about 75° C. for about 2 hours. Then about 319grams of acetone are added at a rate of about 35 ml/min. and the mixtureis allowed to react at 67°-70° C. for another 20 hours. The mixture isthen neutralized with 10% HCl under cooling and the layers areseparated. The organic phase is then evaporated at 10-15 mm Hg/50° C.and is then filtered.

The product has a viscosity at 25° C. of about 306 cps and a refractiveindex at 25° C. of about 1.5484. No free formaldehyde is detected. Theaverage molecular weights are: M_(w) =347, M_(n) =225 (by GPC analysis).

EXAMPLE 2

Example 1 is repeated except that 2.5 moles formaldehyde are added overa period of 20 minutes. The product has a viscosity at 25° C. of about910 cps and a refractive index at 25° C. of about 1.5520. No freeformaldehyde is detected. The average molecular weights are M_(w) =604,M_(n) =282 (by GPC analysis).

EXAMPLE 3

Example 1 is repeated except that 3.75 moles formaldehyde are added overa period of 30 min. The product has a viscosity at 25° C. of about 24stokes and a refractive index at 25° C. of about 1.5511. No freeformaldehyde is detected. The average molecular weights are M_(w) =891,M_(n) =327 (by GPC analysis).

EXAMPLE 4

Example 3 is repeated except that there is no reaction with acetone. Theproduct has a viscosity at 25° C. of about 16.6 stokes and a refractiveindex at 25° C. of about 1.5402. No free formaldehyde is detected. Theaverage molecular weights are M_(w) =809, M_(n) =324 (by GPC analysis).

EXAMPLE 5

Example 4 is repeated except that 501 g methylisobutylketone areemployed in place of methylamylketone. The product has a viscosity at25° C. of about 41 stokes and a refractive index at 25° C. of about1.5255. No free formaldehyde is detected. The average molecular weightsare M_(w) =1525, M_(n) =279 (by GPC analysis).

EXAMPLE 6

Example 5 is repeated except that the formaldehyde is added at 50° C.over a period of 1.5 hrs. After it has reacted for two more hours, 640 gacetone are added at a rate of 100 ml/min. and the mixture is allowed toreact for 6 hrs. at 60° C. The excess acetone is distilled off beforeneutralization. The product has a viscosity at 25° C. of about 539 cpsand a refractive index at 25° C. of about 1.5500. No free formaldehydeis detected. The average molecular weights are M_(w) =479, M_(n) =235(by GPC analysis).

EXAMPLE 7

Example 6 is repeated except that 23.5 g phenol are added to the mixtureprior to the addition of 4.5 moles formaldehyde at 50° C. over a periodof 2.5 hrs. The product has a viscosity at 25° C. of about 175 cps and arefractive index at 25° C. of about 1.5347. No free formaldehyde isdetected. The average molecular weights are M_(w) =620, M_(n) =226 (byGPC analysis).

EXAMPLE 8

Example 1 is repeated except that a disubstituted cyclopentadieneprepared according to Example 2 of application Ser. No. 300,786 isreacted with formaldehyde. The formaldehyde is added over a period ofabout 40 minutes under cooling between about 24° C. and about 40° C. Themixture is then allowed to react for 2 additional hours. The product hasa viscosity at 25° C. of about 120 stokes and a refractive index at 25°C. of about 1.5575. No free formaldehyde is detected.

EXAMPLES 9-16

Foundry sand mixes are prepared by admixing sand with the bindercompositions shown in Tables 1 and 2 below. The resulting foundry sandmixes are then formed into standard AFS tensile test samples using thestandard procedures. The cured samples are tested for tensile strengthand hardness.

                                      TABLE 1                                     __________________________________________________________________________    EXAMPLES 9-16 - COMPOSITION AND TENSILE STRENGTHS                             __________________________________________________________________________    (A) Substituted Cyclopentadiene Polymers                                          Polymer prepared according to Example 1                                                                 64.4                                                Polymer prepared according to Example 2                                                                     64.4                                            Polymer prepared according to Example 3                                                                         64.4                                        Polymer prepared according to Example 4                                                                             64.4                                    Polymer prepared according to Example 5   64.4                                Polymer prepared according to Example 6       64.4                            Polymer prepared according to Example 7           64.4                        Polymer prepared according to Example 8               64.4                (B) Epoxy Resin               27.6                                                                              27.6                                                                              27.6                                                                              27.6                                                                              27.6                                                                              27.6                                                                              27.6                                                                              27.6                    Epon 828 (Shell)                                                          (C) DBE-2 (DuPont)            4.4 4.4 4.4 4.4 4.4 4.4 4.4 4.4                 (D) TXIB (Kodak)              2.7 2.7 2.7 2.7 2.7 2.7 2.7 2.7                 (E) BHT (ppm)                 500 500 500 500 500 500 500 500                 (F) Silane A-186              0.9 0.9 0.9 0.9 0.9 0.9 0.9 0.9                 (G) BF.sub.3.2H.sub.2 O catalyst (% based on binder)                              17.5% BF.sub. 3.2H.sub.2 O/41.25% Glycerine/41.25% PeP                                                  8.2 8.2 8.2                 6.8                     15% BF.sub.3.2H.sub.2 O/42.5% Glycerine/42.5% PeP 450                                                               6.8 6.8 6.8 8.2                     Work Time/Strip Time          28/49                                                                             27/55                                                                             29/55                                                                             27/67                                                                             39/84                                                                             41/85                                                                             23/40                                                                             25/46               Tensiles (PSI)                                                                1 Hr.                         258 275 250  90  65  93 122 108                 3 Hrs.                        338 378 337 140 178 162 158 115                 24 Hrs.                       343 375 362 258 185 187 253 118                 __________________________________________________________________________     "Pep 450" is available from BASF and is a tetrol of about 400 molecular       weight obtained from reacting pentaerythritol with propylene oxide.      

EXAMPLE 17

Part A

Erosion wedge cores are prepared using the compositions and curingtechniques of Examples 10 and 11 hereinabove. The cores are used to havepoured therein gray iron at 2700° F. Only slight to moderate erosion isobserved.

Companion Part B

Part A of Example 17 is repeated except that the binder contains thedisubstituted cyclopentadiene prepared according to Example 2 ofapplication Ser. No. 300,786 instead of the polymers of Examples 10 and11. Severe erosion is observed.

What is claimed is:
 1. Polymeric cyclopentadiene derivative havingrecurring units of the formula I or isomers thereof or mixtures thereof:##STR24## wherein each R₁ and R₂ individually is a hydrocarboncontaining 1 to 10 carbon atoms, or a hydrocarbon containing one or moreoxygen bridges, or a furyl group; or are interconnected and togetherwith the carbon atom to which they are connected form a cycloaliphatichydrocarbon group, or one of R₁ or R₂ is hydrogen; each R₃, R₄, R₅, R₆,and R₉ is individually hydrogen, methyl,--CH₂ --, or ##STR25## providedthat two of R₃, R₅, R₆, and R₄ or R₉ are --CH₂ -- and that at least twoof said R₃, R₄, R₅, R₆, and R₉ are hydrogen; andwherein each R₇ and R₈individually is a hydrocarbon group containing 1 to 10 carbon atoms, ora hydrocarbon group containing one or more oxygen bridges, or areinterconnected and together with the carbon atoms to which they areconnected form a cycloaliphatic hydrogen group, or one of R₇ or R₈ ishydrogen, or R₄ or R₅ or R₉ is: ##STR26## and wherein n is at least 2.2. The derivative of claim 1 wherein at least one of R₁ and R₂ is methyland the other is an alkyl of 2 to 5 carbon atoms.
 3. The derivative ofclaim 1 wherein three of R₃, R₄, R₅, R₆, and R₉ are H.
 4. The derivativeof claim 1 wherein R₁ is methyl and R₂ is isobutyl.
 5. The derivative ofclaim 1 wherein R₁ and R₂ are interconnected and form a cyclohexyl ringwith the common carbon atom to which they are attached.
 6. Thederivative of claim 1 wherein R₁ is methyl and R₂ is ethyl.
 7. Thederivative of claim 1 wherein R₁ and R₂ are phenyl.
 8. The derivative ofclaim 1 wherein R₁ is furyl and R₂ is H.
 9. The derivative of claim 1wherein R₁ and R₂ are isobutyl.
 10. The derivative of claim 1 wherein R₁and R₂ are interconnected and form an isophoronefulvene ring with thecommon carbon atom to which they are connected.
 11. The derivative ofclaim 1 wherein n is an integer of about 2 to about
 9. 12. Thederivative of claim 1 having a molecular weight of about 350 to about1525.
 13. A composition containing at least one polymericcyclopentadiene derivative having recurring units of the formula I orisomers thereof or mixtures thereof: ##STR27## wherein each R₁ and R₂individually is a hydrocarbon containing 1 to 10 carbon atoms or ahydrocarbon containing one or more oxygen bridges in the chain andcontaining up to 10 carbon atoms, or a furyl group; or areinterconnected and together with the carbon atom to which they areconnected form a cycloaliphatic hydrocarbon group or one of R₁ or R₂ ishydrogen and wherein each R₃, R₄, R₅, R₆, and R₉ individually ishydrogen or --CH₂ -- or methyl or ##STR28## or R₄ or R₉ or R₅ is##STR29## wherein each R₇ and R₈ individually is a hydrocarbon groupcontaining 1-10 carbon atoms, or a hydrocarbon containing one or moreoxygen bridges in the chain and containing up to 10 carbon atoms or areinterconnected and together with the carbon atom to which they areconnected form a cycloaliphatic hydrocarbon group; or one of R₇ or R₈ ishydrogen, and provided that at least two of R₃, R₅, R₆, and R₄ or R₉ are--CH₂ -- and that at least two of said R₃, R₄, R₅, R₆, and R₉ arehydrogen; and wherein n is at least 2; and an effective catalytic amountof an acidic catalyst having a pka of about 4 or less.
 14. Thecomposition of claim 13 wherein at least one of R₁ and R₂ is methyl andthe other is an alkyl of 2 to 5 carbon atoms.
 15. The composition ofclaim 13 wherein three of R₃, R₄, R₅, R₆, and R₉ are H.
 16. Thecomposition of claim 15 wherein R₁ is methyl and R₂ is isobutyl.
 17. Thecomposition of claim 15 wherein R₁ and R₂ are interconnected and form acyclohexyl ring with the common carbon atom to which they are attached.18. The composition of claim 15 wherein R₁ is methyl and R₂ is ethyl.19. The composition of claim 15 wherein R₁ and R₂ are phenyl.
 20. Thecomposition of claim 15 wherein R₁ is furyl and R₂ is H.
 21. Thecomposition of claim 15 wherein R₁ and R₂ are isobutyl.
 22. Thecomposition of claim 15 wherein R₁ and R₂ are interconnected and form anisophoronefulvene ring with the common carbon atom to which they areconnected.
 23. The composition of claim 13 wherein n is an integer ofabout 2 to about
 9. 24. The composition of claim 13 wherein saidderivative has a molecular weight of about 350 to about
 1525. 25. Thecomposition of claim 13 wherein the amount of said acidic catalyst is atleast about 0.8% by weight.
 26. The composition of claim 13 wherein saidcatalyst is a Lewis Acid.
 27. The composition of claim 26 wherein saidLewis Acid is BF₃.
 28. A molding composition which comprises a majoramount of aggregate and an effective bonding amount up to about 40% byweight of the aggregate of the composition of claim
 13. 29. The moldingcomposition of claim 28 which is a foundry composition containing up toabout 10% by weight of the aggregate of said composition.
 30. A processfor the fabrication of molded articles which comprises:(a) mixing theaggregate with a bonding amount up to about 40% by weight based upon theweight of the aggregate of a composition of claim 13; (b) introducingthe composition obtained from step (a) into a pattern; (c) hardening thecomposition in the pattern to become self-supporting; and (d) thereafterremoving the shaped article of step (c) from the pattern and allowing itto further cure, thereby obtaining a hardened, solid, cured, moldedarticle.
 31. A process for the fabrication of molded articles whichcomprises:(a) mixing the aggregate with a bonding amount of to about 40%by weight based upon the weight of the aggregate of at least onederivative of claim 1; (b) introducing the composition obtained fromstep (a) into a pattern; (c) hardening the composition in the pattern tobecome self-supporting by passing an acidic gas through the composition;and (d) thereafter removing the shaped article of step (c) from thepattern and allowing it to further cure, thereby obtaining a hardened,solid, cured, molded article.
 32. A process for preparing polymericcyclopentadiene derivative which comprises reacting cyclopentadienederivative having the formula: ##STR30## isomers, or mixtures thereof;wherein each R₁ and R₂ individually is a hydrocarbon containing 1 to 10carbon atoms or a hydrocarbon containing one or more oxygen bridges inthe chain and contains up to 10 carbon atoms; or are interconnected andtogether with the carbon atom to which they are connected form acycloaliphatic hydrocarbon group or one of R₁ or R₂ is hydrogen; eachR₃, R₄, R₅, R₆, and R₉ individually is hydrogen, methyl, or ##STR31## orR₄ or R₉ or R₅ is ##STR32## wherein each R₇ and R₈ individually is ahydrocarbon containing 1 to 10 carbon atoms or a hydrocarbon containingone or more oxygen bridges in the chain and containing up to 10 carbonatoms; or are interconnected and together with the carbon atom to whichthey are connected form a cycloaliphatic hydrocarbon group or furyl orone of R₇ or R₈ is hydrogen, and provided that at least four of R₃, R₄,R₅, R₆, and R₉ are hydrogen; with formaldehyde in the presence of abasic catalyst to provide a polymeric cyclopentadiene derivative;wherein about 0.1 to about 1 mole of formaldehyde per mole of saidcyclopentadiene derivative is employed.
 33. The process of claim 32wherein about 0.25 to about 0.75 moles of formaldehyde per mole of saidcyclopentadiene derivative are employed.
 34. A polymeric cyclopentadienederivative obtained by the process of claim
 32. 35. The process of claim32 wherein said basic catalyst is selected from the group of strongbases, amines and basic ion exchange resins.
 36. The process of claim 32wherein the reaction is carried out at temperatures of about 60°-90° C.in about 5 to about 25 hours.